GB2280265A - Monitoring bulk liquids for presence of an additive - Google Patents
Monitoring bulk liquids for presence of an additive Download PDFInfo
- Publication number
- GB2280265A GB2280265A GB9315129A GB9315129A GB2280265A GB 2280265 A GB2280265 A GB 2280265A GB 9315129 A GB9315129 A GB 9315129A GB 9315129 A GB9315129 A GB 9315129A GB 2280265 A GB2280265 A GB 2280265A
- Authority
- GB
- United Kingdom
- Prior art keywords
- bulk liquid
- chemiluminescent
- additive
- reaction
- amount
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000007788 liquid Substances 0.000 title claims description 43
- 239000000654 additive Substances 0.000 title claims description 34
- 230000000996 additive effect Effects 0.000 title claims description 26
- 238000012544 monitoring process Methods 0.000 title claims description 10
- 239000000126 substance Substances 0.000 claims description 40
- 239000003550 marker Substances 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 8
- 239000003208 petroleum Substances 0.000 claims description 8
- -1 acridinium compound Chemical class 0.000 claims description 7
- 238000004458 analytical method Methods 0.000 claims description 7
- 239000003153 chemical reaction reagent Substances 0.000 claims description 5
- 238000010790 dilution Methods 0.000 claims description 4
- 239000012895 dilution Substances 0.000 claims description 4
- 238000009472 formulation Methods 0.000 claims description 4
- 230000000977 initiatory effect Effects 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000004020 luminiscence type Methods 0.000 claims description 3
- 239000002480 mineral oil Substances 0.000 claims description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 239000002283 diesel fuel Substances 0.000 claims description 2
- 230000002708 enhancing effect Effects 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 239000004615 ingredient Substances 0.000 claims description 2
- 239000010687 lubricating oil Substances 0.000 claims description 2
- 235000010446 mineral oil Nutrition 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 230000009257 reactivity Effects 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 1
- 239000000047 product Substances 0.000 description 14
- 239000000446 fuel Substances 0.000 description 12
- 238000001514 detection method Methods 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- DZBUGLKDJFMEHC-UHFFFAOYSA-N acridine Chemical class C1=CC=CC2=CC3=CC=CC=C3N=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000013459 approach Methods 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000005192 partition Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- BVTJGGGYKAMDBN-UHFFFAOYSA-N Dioxetane Chemical class C1COO1 BVTJGGGYKAMDBN-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical class N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- DZBUGLKDJFMEHC-UHFFFAOYSA-O acridine;hydron Chemical compound C1=CC=CC2=CC3=CC=CC=C3[NH+]=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-O 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 238000003149 assay kit Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000002816 fuel additive Substances 0.000 description 1
- 230000002163 immunogen Effects 0.000 description 1
- 238000010324 immunological assay Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 239000013520 petroleum-based product Substances 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000275 quality assurance Methods 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/003—Marking, e.g. coloration by addition of pigments
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
- C10L1/232—Organic compounds containing nitrogen containing nitrogen in a heterocyclic ring
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M171/00—Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
- C10M171/007—Coloured or dyes-containing lubricant compositions
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M177/00—Special methods of preparation of lubricating compositions; Chemical modification by after-treatment of components or of the whole of a lubricating composition, not covered by other classes
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/76—Chemiluminescence; Bioluminescence
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/26—Oils; Viscous liquids; Paints; Inks
- G01N33/28—Oils, i.e. hydrocarbon liquids
- G01N33/2835—Specific substances contained in the oils or fuels
- G01N33/2882—Markers
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/22—Heterocyclic nitrogen compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/22—Heterocyclic nitrogen compounds
- C10M2215/221—Six-membered rings containing nitrogen and carbon only
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/22—Heterocyclic nitrogen compounds
- C10M2215/225—Heterocyclic nitrogen compounds the rings containing both nitrogen and oxygen
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/22—Heterocyclic nitrogen compounds
- C10M2215/225—Heterocyclic nitrogen compounds the rings containing both nitrogen and oxygen
- C10M2215/226—Morpholines
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/30—Heterocyclic compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/30—Refrigerators lubricants or compressors lubricants
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/32—Wires, ropes or cables lubricants
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/34—Lubricating-sealants
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/36—Release agents or mold release agents
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/38—Conveyors or chain belts
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/40—Generators or electric motors in oil or gas winning field
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/42—Flashing oils or marking oils
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/44—Super vacuum or supercritical use
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/50—Medical uses
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T436/00—Chemistry: analytical and immunological testing
- Y10T436/13—Tracers or tags
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Physics & Mathematics (AREA)
- General Health & Medical Sciences (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Biochemistry (AREA)
- Analytical Chemistry (AREA)
- Food Science & Technology (AREA)
- Medicinal Chemistry (AREA)
- Plasma & Fusion (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
- Investigating Or Analysing Materials By Optical Means (AREA)
- Detergent Compositions (AREA)
Description
2280265 MONITORING OF CHEMICAL ADDITIVES This invention relates to a
method for monitoring the levels of chemical marker compounds and an assay kit enabling the monitoring to be carried out under field or laboratory conditions. The invention is particularly, but not exclusively, directed towards the detection of added chemicals in liquid products, especially In oil based products such as petroleum.
Chemical additives are important constituents of oil based products such as petroleum, diesel oil and lubricating oils. The additives are generally designed to impart favourable and occasionally unique properties to the product such that their absence or a reduction In their concentration may result in a significant loss of performance. These additives are normally introduced at a central distribution point into products which may be distributed on a world wide basis. Since product performance is dependent on the presence of appropriate levels of the additives in the final product as it is retailed, a system for demonstrating their presence at any point in the distribution chain Is required.
A second, but equally important consideration, relates to the problem of counterfeiting. Products which are perceived to have favourable properties over rival products will be imitated for reasons of commercial gain. They may not, for example, enjoy the benefits of the correct additives but may be sold as to imitate visual ly the better product. In such a situation, the ability to distinguish the 2 genuine product from imitations is highly desirable.
Accurate identification of oil based products is also important since litigation can be brought as a consequence of accidents and spillages. In these situations, the presence of a marker substance which can identify or alternatively exclude a particular manufacturer or distributor can be of extreme value.
In summary, the presence of readily identifiable marker substances in oil based products could contribute significantly to several aspects of quality assurance in the oil and petroleum industry. Up to now, it appears that no simple procedure has yet been devised to provide such a system.
Fuel additives are frequently beneficial to the performance of the product at extremely low concentrations. However, their incorporation into fuels at such low concentrations means that they are not readily detected by conventional analytical procedures. Even in situations where the additive can be detected by sophisticated physical/chemical techniques, there is the problem that samples must be taken to a central laboratory for analysis which may be tedious and time consuming.
One recent approach has been to make use of the fact that many organic compounds are immunogenic so that immunological assay methods can be applied to their detection (see for example EP-A-0327163). Though these methods do possess inherently high sensitivities, they are not intrinsically simple to perform and therefore do not 3 lend themselves to analysis in the field. moreover, they involve the use of monoclonal antibodies which may lack the stability of simple chemicals, again restricting the site or scope of application. This approach relies an subjecting a small sample to an assay procedure to quantify the additive compound of interest; there is no suggestion of introducing a chemical marker to the bulk product or along the distribution chain at source which is subsequently triggered possibly many weeks later several steps down the distribution chain to allow analysis or detection thereof.
We have developed a radically different approach which uses an independent substance which has some unique, easily detected property and which can be added to the fuel at source or along the distribution chain as a marker along with the additives. The marker should possess certain characteristics. Firstly, it should partition into the organic phase so that contact with water, as might occur for example in a storage vessel, will not cause substantial partitioning into the aqueous phase. Secondly, the marker compound should remain stable in the fuel for several weeks without substantial alteration of its detection characteristics. Thirdly, the marker compound should be reproducibly detectable at extremely low concentrations, partly for reasons of cost but also to ensure that it does not itself interfere with the performance of the fuel. The marker compound should be detectable quantitatively with a simple detection system. Finally, neither the fuel itself or any other additive should interfere significantly with the 4 behaviour of the marker under normal analytical conditions.
Accordingly, in one aspect of this invention, there is provided a method for allowing authentication of a bulk liquid, which comprises introducing into said bulk liquid a chemiluminescent substance capable of taking part In a chemiluminescent reaction, exposing samples for authentication to the conditions required to trigger said chemiluminescence reaction, and monitoring whether said reaction occurs.
Chemiluminescent compounds have the property that, under defined conditions, they can be induced to emit light. This process can involve activation of a reaction by the supply of heat to the compound or alternatively may involve a simple chemical triggering mechanism. The light emission can be detected or quantified using a simple photon counting device. One potential advantage of chemiluminescence is that, generally, endogenous chemiluminescence is low so that a small signal can be readily detected against a very low background.
The term "bulk liquid" is used to define any liquid to be authenticated. Whilst primarily Intended to cover industrial liquids such as mineral oils intended to be supplied In large volumes, the term is also intended to enbrace liquids supplied in small volumes, other than for analytical purposes. The chemiluminescent substance may be any suitable substance which retains at least some of its chemiluminescence when introduced with said bulk liquid, and Includes those chemiluminescent materials referred to as bioluminescent. The terms uchemiluminescent substance" and the like should be interpreted broadly as including chemiluminescent compounds as well as cofactors, catalysts or other substances capable of taking part in a 5 chemiluminescent reaction.
In another aspect, this invention provides a method of detecting subsequent dilution of a sample of bulk liquid which comprises introducing Into said undiluted bulk liquid a known amount of a chemiluminescent marker substance, taking a sample of said bulk liquid, Initiating the chemiluminescent reaction in said sample, monitoring the characteristics of said reaction, comparing said characteristics with those corresponding to the undiluted bulk liquid, to determine the extent (If any) of dilution of said bulk liquid.
In a further aspect, this Invention provides a method of treating a bulk liquid to allow subsequent identification, analysis, or determination of the presence of an additive therein, which comprises introducing into said bulk liquid an amount of a chemiluminescent marker substance indicating the presence of, or related to the amount of, said additive.
Said chemiluminescent marker substance is preferably Introduced into said bulk liquid with said additive. The additive may comprise just one or a plurality of additive substances.
The methods of this invention are particularly useful when said bulk liquid is a mineral oil based product, 6 although It may be any industrial or non-industrial liquid. Thus, the methods of this invention relate to the use of a chemiluminescent marker which can be incorporated into the fuel at sufficiently low concentrations that it does not affect performance, and which can also be reliably detected using a simple analytical kit.
A preferred aspect of the invention involves the use of chemiluminescent acridinium compounds which have inherently high quantum yields and can therefore be detected with extremely high sensitivity. The application of these compounds as labels for substances of biological Interest is disclosed in UK-B-2112779.
Somewhat surprisingly, certain acridinium compounds can be detected with high sensitivity in petroleum by means of addition of simple oxidising reagents, the light output being directly proportional to the concentration of acridinium compound in the sample. A critical observation is that a 10pl sample of petrol yielded no significant chemiluminescence when subjected to the reagents used to generate the light emitting reaction.
The chemiluminescent marker substance is preferably an acrIdinium compound capable of undergoing a chemiluminescent reaction and of the general formula:- R, X 1 + N R, I,- G) "e ?1 1 4--)Y() wherein R, is a moiety capable of beIng part of a quaternary 1 7 nitrogen centre, for example an alkyl, alkenyl, alkynyl, alkoxyl or aryl containing group.
R2 and R. may be the same as R, or a hydroxyl, carboxyl, amino, substituted amino or halide group, R4 is a moiety whose chemical reactivity permits the compound to undergo a chemiluminescent reaction.
The chemiluminescent marker substance is substantially insoluble in water. Said chemiluminescent marker substance is preferably present in said bulk liquid in an amount between 0.001 ng/)ll and 10 ng/pl, and preferably is immunologically unbound in normal use of said bulk liquid.
In another aspect, this invention provides an additive formulation for a bulk liquid, said formulation containing one or more ingredients for modifying or enhancing one or more selected properties of the bulk liquid, in combination with an amount of a chemiluminescent marker substance.
In a further aspect, this invention provides a method of identifying or analysing a bulk liquid to determine the presence or quantity of an additive or other material present in small quantities, the bulk liquid including an amount of a chemiluminescent substance indicating the presence of, or related to the amount of, said additive or other material, which method comprises initiating the chemiluminescent reaction and observing the characteristics of said reaction to determine the presence and/or concentration of said additive or other material.
The observed characteristics may comprise one or more of wavelength, intensity, variation of intensity with time, 8 other kinetic variations, and polarisation.
The invention may make use of other chemiluminescent compounds such as (though not exclusively) phthalhydrazides and their derivatives, phenanthridinium and quinolinium salts, bis-acridinium salts, bis-oxalate esters, dioxetanes and organometallic compounds such as ruthenium chelates. The structures of numerous chemiluminescent compounds are recited in the literature and the selection of suitable compounds in accordance with the detailed criteria contained herein is well within the competance of one skilled in the art.
Our experiments have shown that such compounds may be stored In petroleum for significant periods of time with no loss of chemiluminescent properties. Moreover, we have found that such compounds can be designed so that they will not partition into water should such contamination be present In storage vessels. Finally we have been able to detect as little as 1.2 parts/billion of the acridinium compound in 10pl of petroleum.
These observations demonstrate that chemiluminescent molecules and in particular acridinium, compounds can be used as marker substances In petroleum based products. It is thus possible to add such compounds to petrol at the same time as other, performance related additives are being Introduced. Analysis of the amount of chemiluminescent substance at any point in the distribution chain will thus provide an indication such addition has been made and also that the fuel has not been diluted with other base fuel. Moreover, t 9 the presence of the chemiluminescent molecule in the fuel will indicate that the fuel is the genuine manufactured material.
In practice, as little as lg of a chemiluminescent acridinium derivative can be added to a volume of 1.5 million litres of petroleum and be readily detected after a period of 6 weeks in only 10 pl of fuel. At the concentration of acridinium compound present, there is no detectable effect of the marker on performance. Thus, at this stage, it appears that the use of chemiluminescent markers in fuel offers a simple, reliable and sensitive method for monitoring additive levels.
A further aspect of the invention relates to a test kit for the monitoring of additive levels under field conditions. Luminometers capable of detecting low levels of light emission have been available for several years, though most such Instruments are designed for routine laboratory use. Hand held devices have been developed which are capable of reading the light emission from constant sources by means of a photographic plate. In this aspect, the invent ion provides a luminescence detector including Injection devices capable of delivering the reagents necessary to initiate the chemiluminescent reaction. The detector is preferably capable of fitting into a compartment no bigger than a brief case. The light emission is recorded and, If below a certain threshold, will alert the operator to the possibility that the additive level is inadequate. Further tests can then be undertaken In the laboratory to determine the exact nature of the defective level.
The invention will now be further described with reference to the following example:Examnle The following compounds (1) and (2) were prepared by standard methods:- 0 cmi Cf3 st- (0 1 ( P.) C-,,,5 C','SS03- + C --0 C zo +C C 141 C=0 r_ 0 9 0 t2,r Approximately one hundred pg of each compound were dissolved in 10 ml of dry acetonitrile. Ten pl of each solution were then diluted to a volume of 1 ml with standard unleaded petrol to give a final concentration of acridinium salt of approximately 100 nglml. These samples were then stored at room temperature in the dark and, at intervals, 10 pl aliquots of these were removed to measure chemiluminescence. Measurements were carried out in a Berthold "Klinilumatn Luminometer. The chemiluminescent reaction was initiated by injection of 0.3 ml of a solution of 1% hydrogen peroxide In 0.1 M nitric acid followed by 0.3 ml of a solution of 1.0% 11 sodium hydroxide containing 0.2% cetyltrimethylammonium chloride. Luminescence output was integrated over a suitable interval and results obtained after different periods of storage were as follows:
CO ound 1 Coffipound 2 Time Day 1 Day 10 Day 27 Day 33 Day 40 Day 1 Day 2 Day 4 Day 10 Day 17 Light Yield (RLU) l. S X 107 1. 5 X 107 1. 4 x 107 1. 3 x 107 1. 3 x 107 2.4 x 107 2.3 x 107 2.4 x 107 2.5 x 107 2.0 x 10 These results show that when either of these compounds is added to standard unleaded petrol, chemiluminescence can be recovered quantitatively within reasonable limits of experimental error over a significant time period.
12
Claims (14)
1. A method for allowing authentication of a bulk liquid, which comprises introducing into said bulk liquid a chemiluminescent substance capable of taking part in a chemiluminescent reaction, exposing samples for authentication to the conditions required to trigger said chemiluminescence reaction, and monitoring whether said reaction occurs.
2. A method of detecting subsequent dilution of a sample of bulk liquid which comprises introducing into said undiluted bulk liquid a known amount of a chemiluminescent marker substance, taking a sample of said bulk liquid, Initiating the chemiluminescent reaction in said sample, monitoring the characteristics of said reaction, comparing said characteristics with those of the undiluted bulk liquid, to determine the extent of dilution of said bulk liquid.
3. A method of treating a bulk liquid to allow subsequent identification, analysis, or determination of the presence of an additive therein, comprises introducing into said bulk liquid an amount of a chemiluminescent marker substance Indicating the presence of, or related to the amount of, said additive.
4. A method according to Claim 3, wherein said chemiluminescent marker substance is introduced into said bulk liquid with said additive.
5. A method according to Claim 3 or 4, wherein said 13 additive comprises a plurality of additive substances.
6. A method according to any preceding claims, wherein said bulk liquid is a mineral oil based product.
7. A method according to Claim 6, wherein said bulk liquid is selected from the group comprising petroleum, diesel oil and lubricating oils.
8. A method according to any preceding claim, wherein said chemiluminescent marker substance is an acridinium compound capable of undergoing a chemiluminescent reaction 10 and of the general formula:- 1 X 1 + I'- N R) , _ Y c, 3 """,4 0 cc wherein R, is a moiety capable of being part of a quaternary nitrogen centre, R. and R3 may be the same as R, or a hydroxyl, carboxyl, amino, substituted amino or halide group, R4 is a moiety whose chemical reactivity permits the compound to undergo a chemiluminescent reaction.
9. A method according to any preceding claim, wherein said chemiluminescent marker substance is substantially insoluble In water. 20
10. A method according to any preceding claim, wherein 14 said chemiluminescent marker substance Is present in said bulk liquid in an amount between 0.001 ng/pl and 10 ng/pl.
11. A method according to any preceding claim, wherein the chemiluminescent marker substance is immunologically unbound in normal use of said bulk liquid.
12. An additive formulation for a bulk liquid, said formulation containing one or more ingredients for modifying or enhancing one or more selected properties of the bulk liquid in combination with an amount of a chemiluminescent marker substance.
13. A method of identifying or analysIng a bulk liquid to determine the presence or quantity of an additive or other material present in small quantities, the bulk liquid including an amount of a chemiluminescent substance Indicating the presence of, or related to the amount of, said additive or other material, which method comprises initiating the chemiluminescent reaction and observing the characteristics of said reaction to determine the presence and/or concentration of said additive or other material.
14. A kit for determining the presence or concentration of an additive in a sample of bulk liquid, comprises a luminescense detector for detecting luminescence of a sample in a sample container, means for injecting with said sample container the reagent or reagents necessary to initiate the chemiluminesence reaction and means for indicating or recording the level of luminesence detected.
1
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB9315129A GB2280265B (en) | 1993-07-21 | 1993-07-21 | Monitoring of chemical additives |
ES94305186T ES2184752T3 (en) | 1993-07-21 | 1994-07-15 | MONITORING OF CHEMICAL ADDITIVES. |
EP94305186A EP0637743B1 (en) | 1993-07-21 | 1994-07-15 | Monitoring of chemical additives |
DE69431506T DE69431506T2 (en) | 1993-07-21 | 1994-07-15 | Monitoring chemical additives |
US08/842,118 US5879946A (en) | 1993-07-21 | 1997-04-28 | Monitoring of chemical additives |
HK98115336A HK1014046A1 (en) | 1993-07-21 | 1998-12-24 | Monitoring of chemical additives |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB9315129A GB2280265B (en) | 1993-07-21 | 1993-07-21 | Monitoring of chemical additives |
Publications (3)
Publication Number | Publication Date |
---|---|
GB9315129D0 GB9315129D0 (en) | 1993-09-01 |
GB2280265A true GB2280265A (en) | 1995-01-25 |
GB2280265B GB2280265B (en) | 1997-06-04 |
Family
ID=10739204
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB9315129A Revoked GB2280265B (en) | 1993-07-21 | 1993-07-21 | Monitoring of chemical additives |
Country Status (6)
Country | Link |
---|---|
US (1) | US5879946A (en) |
EP (1) | EP0637743B1 (en) |
DE (1) | DE69431506T2 (en) |
ES (1) | ES2184752T3 (en) |
GB (1) | GB2280265B (en) |
HK (1) | HK1014046A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6043505A (en) * | 1998-08-06 | 2000-03-28 | Ames; Donald P. | Device and method for monitoring fluids with a detection of cross sectional shape of transmitted beam |
GB2344599A (en) * | 1998-12-10 | 2000-06-14 | John Hogg Technical Solutions | Method for marking liquids and compounds for use in said method |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2312746B (en) * | 1996-04-24 | 2000-07-19 | Molecular Light Technology Lim | Detection of an analyte in a Water Immiscible Solvent |
US7370797B1 (en) | 1996-05-31 | 2008-05-13 | Scott Lindsay Sullivan | Pill printing and identification |
US6490030B1 (en) * | 1999-01-18 | 2002-12-03 | Verification Technologies, Inc. | Portable product authentication device |
US20040024784A1 (en) * | 2002-04-09 | 2004-02-05 | Spall Walter Dale | Information system for manipulating data related to the ordering and performance of services and communication of results |
USH2257H1 (en) * | 2005-09-28 | 2011-06-07 | The United States Of America As Represented By The Secretary Of The Navy | Microtags for detection and identification of materials |
US8129190B2 (en) * | 2006-11-17 | 2012-03-06 | Applied Nanotech Holdings, Inc. | Tagged petroleum products and methods of detecting same |
Citations (3)
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US4764290A (en) * | 1987-02-02 | 1988-08-16 | National Identification Laboratories, Inc. | Identification marking of oils |
EP0512404A1 (en) * | 1991-05-03 | 1992-11-11 | Nalco Chemical Company | Identification of liquid hydrocarbons using chemical markers |
GB2261509A (en) * | 1991-11-13 | 1993-05-19 | Ethyl Petroleum Additives Inc | Indicator systems for additives present in hydrocarbon fluid |
Family Cites Families (8)
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JPS55131754A (en) * | 1979-04-03 | 1980-10-13 | Yamanouchi Pharmaceut Co Ltd | Method and dvice for detecting fluorescent substance |
EP0082636B2 (en) * | 1981-12-11 | 2006-10-18 | The Welsh National School of Medicine | Luminescent labelling materials and procedures |
FR2611064B1 (en) * | 1987-02-13 | 1989-06-16 | Schvoerer Max | METHOD OF MARKING OBJECTS BY MICRO-CRYSTALS WITH MEMORY EFFECT AND MARKERS FOR IMPLEMENTING SAME |
US4793977A (en) * | 1987-04-09 | 1988-12-27 | Cape Cod Research, Inc. | Colorimetric detector for monitoring oil degradation |
US4927769A (en) * | 1987-07-08 | 1990-05-22 | Ciba Corning Diagnostics Corp. | Method for enhancement of chemiluminescence |
GB8802237D0 (en) * | 1988-02-02 | 1988-03-02 | Shell Int Research | Detection of chemicals by immunoassay |
US5470754A (en) * | 1992-06-01 | 1995-11-28 | The Coca-Cola Company | Method and system for sampling and determining the presence of compounds |
GB9218131D0 (en) * | 1992-08-26 | 1992-10-14 | Slater James H | A method of marking a liquid |
-
1993
- 1993-07-21 GB GB9315129A patent/GB2280265B/en not_active Revoked
-
1994
- 1994-07-15 ES ES94305186T patent/ES2184752T3/en not_active Expired - Lifetime
- 1994-07-15 DE DE69431506T patent/DE69431506T2/en not_active Expired - Lifetime
- 1994-07-15 EP EP94305186A patent/EP0637743B1/en not_active Expired - Lifetime
-
1997
- 1997-04-28 US US08/842,118 patent/US5879946A/en not_active Expired - Fee Related
-
1998
- 1998-12-24 HK HK98115336A patent/HK1014046A1/en not_active IP Right Cessation
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4764290A (en) * | 1987-02-02 | 1988-08-16 | National Identification Laboratories, Inc. | Identification marking of oils |
EP0512404A1 (en) * | 1991-05-03 | 1992-11-11 | Nalco Chemical Company | Identification of liquid hydrocarbons using chemical markers |
GB2261509A (en) * | 1991-11-13 | 1993-05-19 | Ethyl Petroleum Additives Inc | Indicator systems for additives present in hydrocarbon fluid |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6043505A (en) * | 1998-08-06 | 2000-03-28 | Ames; Donald P. | Device and method for monitoring fluids with a detection of cross sectional shape of transmitted beam |
GB2344599A (en) * | 1998-12-10 | 2000-06-14 | John Hogg Technical Solutions | Method for marking liquids and compounds for use in said method |
Also Published As
Publication number | Publication date |
---|---|
DE69431506D1 (en) | 2002-11-14 |
GB9315129D0 (en) | 1993-09-01 |
EP0637743B1 (en) | 2002-10-09 |
ES2184752T3 (en) | 2003-04-16 |
HK1014046A1 (en) | 1999-09-17 |
DE69431506T2 (en) | 2003-07-10 |
EP0637743A1 (en) | 1995-02-08 |
GB2280265B (en) | 1997-06-04 |
US5879946A (en) | 1999-03-09 |
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Legal Events
Date | Code | Title | Description |
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773K | Patent revoked under sect. 73(2)/1977 |
Free format text: PATENT REVOKED ON 20040723 |